CN101298045A - Metal/titanic oxide catalyst for catalytic oxidation and preparation thereof - Google Patents
Metal/titanic oxide catalyst for catalytic oxidation and preparation thereof Download PDFInfo
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- CN101298045A CN101298045A CNA2008101239245A CN200810123924A CN101298045A CN 101298045 A CN101298045 A CN 101298045A CN A2008101239245 A CNA2008101239245 A CN A2008101239245A CN 200810123924 A CN200810123924 A CN 200810123924A CN 101298045 A CN101298045 A CN 101298045A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 239000002184 metal Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 21
- 230000003647 oxidation Effects 0.000 title claims abstract description 20
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims description 22
- 150000004706 metal oxides Chemical class 0.000 title claims description 10
- 239000000243 solution Substances 0.000 claims abstract description 52
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000010936 titanium Substances 0.000 claims abstract description 22
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 14
- 230000005855 radiation Effects 0.000 claims abstract description 9
- 239000003381 stabilizer Substances 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 238000002604 ultrasonography Methods 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 229910044991 metal oxide Inorganic materials 0.000 claims description 9
- 239000004408 titanium dioxide Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 239000013049 sediment Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- 125000005270 trialkylamine group Chemical group 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical group [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical group [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 abstract description 2
- 230000004913 activation Effects 0.000 abstract 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 15
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- 230000001684 chronic effect Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- AILDTIZEPVHXBF-UHFFFAOYSA-N Argentine Natural products C1C(C2)C3=CC=CC(=O)N3CC1CN2C(=O)N1CC(C=2N(C(=O)C=CC=2)C2)CC2C1 AILDTIZEPVHXBF-UHFFFAOYSA-N 0.000 description 1
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 206010028400 Mutagenic effect Diseases 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 244000308495 Potentilla anserina Species 0.000 description 1
- 235000016594 Potentilla anserina Nutrition 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- -1 hydroxyl radical free radical Chemical class 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000243 mutagenic effect Toxicity 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical class [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- HDUMBHAAKGUHAR-UHFFFAOYSA-J titanium(4+);disulfate Chemical class [Ti+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HDUMBHAAKGUHAR-UHFFFAOYSA-J 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000759 toxicological effect Toxicity 0.000 description 1
- 239000003053 toxin Substances 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
- 108700012359 toxins Proteins 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention relates to a metal/ titanic dioxide catalyst used for catalytic oxidation and a preparation method thereof. The method is mainly characterized in that: the salt of metal source is dissolved in glycol and added with a stabilizer and a structural directing molecule after being mixed with the solution of titanium source, thus acquiring a mixed solution; the solution is radiated to be evenly distributed by ultrasound and certain energy is used for radiating the solution; in the conditions of radiation and refluence, the mixed solution is stirred and added with an alkali liquor and continuously to be stirred after the adding of the alkali liquor is finished; the solution is taken out, cooled, filtered, washed and dried, thus obtaining the catalyst which consists of metal and titanic dioxide; and a molar ratio of the metal and the titanic dioxide is 0.05: 1-10: 1. The catalyst has the advantages of simple preparation and convenient operation, active components which are not easily lost, wide applicable pH range, and high catalytic activation, etc., thus being a good catalyst in certain advanced catalytic oxidation processes and has good performance by the test of samples.
Description
Technical field:
The present invention relates to a kind of Catalysts and its preparation method, refer more particularly to a kind of metal/titanium dioxide (M/TiO that the catalytic oxidation coupling technique is used for degradation of organic waste water technology that is used for
2) Catalysts and its preparation method.
Background technology:
Along with the continuous development of modern chemistry industry, the value volume and range of product that enters the hardly degraded organic substance in the water body by all means sharply increases, and water environment has been caused serious pollution, is directly threatening human beings'health.The importance of the environmental hazard of these toxic organic chemical product shows chemical carcinogenesis, teratogenesis, mutagenic effect, promptly with ecologic food chain toxicological effect, environment " feminize " effect, inspire red tide and algae effects of toxins etc.In engineering of water treatment, the waste water that contains hardly degraded organic substance is difficult to adopt bioanalysis to be handled usually, chemical constitution that it is stable and bio-toxicity have hindered the metabolism of microorganism, thereby the focus that is treated as water treatment field research and the difficult point of hardly degraded organic substance waste water, generally take chemistry, materialization or high-level oxidation technology etc. with it removal more.Photocatalysis is as studying more high-level oxidation technology this year, can effectively destroy many Stability Analysis of Structures, be difficult to biodegradable organic pollution, and non-secondary pollution thing, contain in processing and have good prospect aspect the organic Industrial Wastewater Treatment of difficult degradation, the research and the application of photocatalysis oxidation technique all paid much attention in countries in the world.
At present, the method for preparing nano titanium oxide mainly contains: the oxyhydrogen flame pyrohydrolysis is sent out, TiCl
4Vapour phase oxidation process, alkoxytitanium vapor phase hydrolysis are sent out with the liquid phase water solution etc., but shortcomings such as these method ubiquities investments are high, technical difficulty is big, long what productive rate of production cycle.And normal optical catalyst TiO
2There is certain defective,, only can absorbs ultraviolet light as greater band gap, low to the sunshine utilization rate, the rate of load condensate height of photo-generated carrier, photocatalysis efficiency is lower.Also exist the reaction time long in the photochemical catalytic oxidation process, the efficiency of light energy utilization is not high, shortcomings such as cost height.These shortcomings have seriously restricted the application in practice of this technology, though there is patent that it is carried out modification, as Chinese patent " preparation method of load type photocatalyst of titania modified by Argentine " (Granted publication CN100360227C) and " multi-functional TiO
2The preparation method of modified light catalyst " (publication number: CN101028592), but preparation method is had relatively high expectations, the catalytic oxidation effect is strong inadequately, and catalyst photocatalysis oxidation reaction required time is still longer, so preparation method is simple, photocatalytic activity is higher and its photocatalysis oxidation reaction time is shortened is current problem demanding prompt solution.
Summary of the invention:
Purpose of the present invention is exactly not high in order to solve normal optical catalyst efficient, and the catalysis time is problem such as length and partially modified catalyst preparation method complexity, and a kind of metal/titanium dioxide (Metal/TiO that is used for catalytic oxidation is provided
2Be called for short M/TiO
2) catalyst, another object of the present invention provides above-mentioned Preparation of catalysts method.
Technical scheme of the present invention is: a kind of metal/titanium dioxide (Metal/TiO that is used for catalytic oxidation
2Be called for short M/TiO
2) catalyst, it is characterized in that forming by metal and titanium dioxide, the mol ratio of metal and titanium dioxide is 0.05: 1-10: 1, wherein said metal is at least a kind of in manganese, iron, copper, zinc, vanadium, rhodium, palladium, gold or the platinum.
The present invention also provides above-mentioned M/TiO
2The Preparation of catalysts method, its concrete preparation process is as follows:
A, metal source salt are dissolved in the ethylene glycol, obtain metal salt solution, and the molar concentration of metal salt solution is 0.001-5mol/L;
B, preparation titanium source solution, its molar concentration is 0.001-10mol/L;
After the titanium source solution of C, the metal salt solution that steps A is made and step B preparation mixes, add stabilizing agent again and structure instructs agent, obtain mixed solution;
D, disperse mixed solution with ultrasound wave irradiation, again with this solution of electromagnetic wave radiation;
E, under irradiation and counterflow condition, add alkali lye while stirring, alkali lye adds the back that finishes to be continued electromagnetic wave radiation and refluxes and also stir;
F, with solution cooling, filter, sediment is spent deionised water again with the acetone washing, oven dry promptly obtains required catalyst.
The salt of metal source described in the steps A is at least a kind of of the nitrate of manganese, iron, copper, zinc, vanadium, rhodium, palladium, gold, platinum or sulfate, is dissolved in the ethylene glycol its one or more, obtains metal source solution.Titanium source described in the step B is titanium tetrachloride, titanium sulfate or butyl titanate.
Wherein the stabilizing agent described in the step C is sodium acetate or sodium acid carbonate, and its molar concentration is between the 0.001-0.5mol/L, and the addition of stabilizing agent is that benchmark adds 1-500mL for the solution of originating with every liter of titanium; It is a kind of of trialkylamine or tetraalkylammonium hydroxide or its mixture that structure instructs agent, and molar concentration is respectively 0.001-5mol/L, and it is that benchmark adds 1-600mL with every liter of titanium source solution that structure instructs the addition of agent.
The ultrasonic solution that makes of usefulness described in the step D is evenly distributed, supersonic frequency is between the 25KHz-130KHz, and be 5-60min service time, is this solution of electromagnetic wave radiation of 520MHz-280GHz then with frequency, the electromagnetic wave input power is 100W-20000W, and exposure time is 1min-30min.
Alkali lye described in the step e is ammoniacal liquor, NaOH or KOH solution, and preferred ammoniacal liquor contains ammonia 15%-28%, and the molar concentration of NaOH or KOH solution is 0.01-5mol/L; The pH value of the addition control solution of alkali lye is 5-12; Alkali lye adds the back that finishes to be continued the irradiation backflow and stirs 1-30min.Bake out temperature described in the step F is 50-120 ℃.
The M/TiO of made of the present invention
2Catalyst, preparation method is simple, does not need the calcining of HTHP or Muffle furnace, and the catalyst of producing not only can be used for ultraviolet catalytic oxidation, is mainly used in external energy and ultraviolet cooperating catalytic oxidation.TiO
2On metal active point position, be in and go back ortho states, can not only be as the active component of photochemical catalytic oxidation, the generation hydroxyl radical free radical can also be stimulated as the avtive spot of external energy, two kinds of effects are collaborative, improved the ability of handling waste water greatly, shortened the time of handling waste water.
Beneficial effect:
This catalyst is made simple, and is easy to operate, and do not need calcinings such as Muffle furnace, and have high catalytic activity and very short advantages such as reaction time, in some senior catalytic oxidation process a kind of good catalyst, through the sample test function admirable.
1, the M/TiO for preparing
2Catalyst grain size is even, with the catalyst particle size of this method preparation between 10-100nm.
2, the M/TiO for preparing
2The catalyst effect is higher; The hardly degraded organic substance that p-nitrophenyl etc. contain phenyl ring has good effect of removing, is a kind of catalyst for catalytic oxidation of broad spectrum type, has broad application prospects.
3, the M/TiO for preparing
2Catalyst, under the synergy of ultraviolet light and external energy, the reaction time shortens greatly; General TiO
2Photochemical catalytic oxidation needs more than 1 hour at least, and the catalyst of preparing with the present invention can shorten to the reaction time the former 1/3-1/20 that takes time under the synergy of ultraviolet and external energy.
4, the active component of mixed sintering in catalyst manufacturing process keeps in course of reaction better; The long-time use, catalyst still keeps higher catalytic activity, and this illustrates that this catalyst has good stable and long service life.
5, preparation method simple, save time, energy-conservation, production efficiency is high and do not need the Muffle furnace calcining, has saved cost.
The M/TiO that the inventive method is made
2The catalyst activity height, uniform ingredients, uniform particle diameter, the catalysis required time is short, and cost is lower, and the production efficiency height is for actual the applying of the collaborative method for treating water of ultraviolet light and external energy source played important impetus.
Description of drawings:
Fig. 1 is Cu/TiO
2Catalyst degradation nitrobenzene is variation diagram in time.
Fig. 2 is Zn, Pd/TiO
2Catalyst degradation chlorobenzene TOC is variation diagram in time.
The specific embodiment:
1, prep solution, dissolving nitric acid mantoquita in the spent glycol, molar concentration is 0.05mol/L; 2, titanium tetrachloride solution, its molar concentration are 1mol/L; 3, with above-mentioned two kinds of solution by the mol ratio in mantoquita and titanium source be mix at 0.05: 1 after, the SAS that adds the 20mL molar concentration in the solution of every liter of titanium source and be 0.01mol/L is as stabilizing agent, and the molar concentration that adds 50mL in every liter of titanium source solution instructs the agent trialkylamine for the 0.3mol/L structure; 4, be that the ultrasound wave irradiation solution irradiation 6min of 33KHZ is evenly distributed it with frequency, incoming frequency is this solution of 100W electromagnetic wave energy irradiation for 800MHz power afterwards, and exposure time is 30min; 5, under irradiation and counterflow condition, add NaOH solution while stirring, molar concentration is 0.01mol/L, and the pH value of control solution is 7, and alkali lye adds the back that finishes to be continued to stir 10min, at step 5 operating period energy chronic exposure 30min; 6, solution is taken out, cooling, filtration are washed sediment with acetone, spend deionised water again, in 55 ℃ of oven dry, promptly obtain Cu/TiO
2Catalyst, wherein Cu and TiO
2Mol ratio be 0.05: 1.
With the catalyst that this method is produced, get 0.1g and put into quartz reactor, adding concentration is the nitrobenzene simulated wastewater 30mL of 200mg/L, under the synergy of ultraviolet light and external energy, can reach the nitrobenzene clearance more than 95% within the 5min.The results are shown in Figure 1.
Embodiment 2:
1, prep solution, the preparation molar concentration is respectively the mixed solution of two kinds of metallic salts of palladium nitrate salt of the nitric acid zinc salt of 1mol/L and 1mol/L in the spent glycol; 2, prepare the titanium source that titanium tetrachloride and butyl titanate mix, its molar concentration is respectively 3mol/L and 5mol/L, and making total mol ratio in metallic salt and titanium source is 0.125: 1; 3, with after above-mentioned two kinds of solution mixing, it is that the sodium acid carbonate of 0.1mol/L is as stabilizing agent that the solution in every liter of titanium source adds the 50mL molar concentration, add structure again and instruct agent, the mixture of trialkylamine and tetraalkylammonium hydroxide, concentration is respectively 0.5mol/L and 1mol/L, and adding total amount is that every liter of titanium source solution adds 200mL; 4 usefulness 40KHZ ultrasound wave irradiation solution 30min are evenly distributed it, are this solution of electromagnetic wave radiation of 1000W with frequency for the 900MHz input power afterwards, and exposure time is 15min; 5, under irradiation and counterflow condition, add KOH solution while stirring, molar concentration is 4mol/L, and the pH value of control solution is 6, and alkali lye adds the back that finishes to be continued to stir 15min, at step 5 operating period energy chronic exposure 15min; 6, solution is taken out, cooling, filtration are washed sediment with acetone, spend deionised water again, in 80 ℃ of oven dry.Promptly obtain Zn.Pd/TiO
2Catalyst, wherein Zn, Pd and TiO
2Mol ratio be 0.125: 1.
With the catalyst that this method is produced, get 0.3g and put into quartz reactor, adding concentration is the chlorobenzene simulated wastewater 30mL of 100mg/L, under the synergy of ultraviolet light and external energy, can reach the chlorobenzene TOC clearance more than 85% within the 10min.The results are shown in Figure 2.
Embodiment 3:
1, prep solution, the combination of dissolving sulphate of iron and platinic sulfate salt in the spent glycol, its molar concentration is respectively 4.5mol/L and 0.002mol/L; 2, prepare the titanium source material of four titanium sulfates, its molar concentration is 1mol/L, and the mol ratio that makes metallic salt and titanium source was at 3: 1; 3, with after above-mentioned two kinds of solution mixing, add sodium acetate as stabilizing agent, its molar concentration is 0.5mol/L, addition is that every liter of titanium source solution adds 200mL, add tetraalkylammonium hydroxide again and instruct agent as structure, its molar concentration is 3mol/L, and addition is that every liter of titanium source solution adds 5mL; 4, with 80KHZ ultrasound wave irradiation solution irradiation 30min it being evenly distributed, is this solution of 10000W electromagnetic wave radiation with 900MHz energy input power afterwards, first irradiation 10min; 5, under irradiation and counterflow condition, add the concentrated ammonia liquor that contains ammonia 20% while stirring, control pH value is 8, adds the back that finishes and continues to stir 30min, at step 5 operating period energy chronic exposure 30min; 6, solution is taken out, cooling, filtration are washed sediment with acetone, spend deionised water again, in 105 ℃ of oven dry.Promptly obtain described catalyst Fe .Pt/TiO
2, wherein Fe, Pt and TiO
2Mol ratio be 3: 1.
Claims (8)
1, a kind of metal/titanium dioxide catalyst that is used for catalytic oxidation, it is characterized in that forming by metal and titanium dioxide, the mol ratio of metal and titanium dioxide is 0.05: 1-10: 1, and wherein said metal is at least a kind of in manganese, iron, copper, zinc, vanadium, rhodium, palladium, gold or the platinum.
2, a kind of Preparation of catalysts method as claimed in claim 1, its concrete preparation process is as follows:
A, metal source salt is dissolved in the ethylene glycol, obtains metal salt solution, the molar concentration of metal salt solution is 0.001-5mol/L;
B, preparation titanium source solution, its molar concentration is 0.001-10mol/L;
After the titanium source solution of C, the metal salt solution that steps A is made and step B preparation mixes, add stabilizing agent again and structure instructs agent, obtain mixed solution;
D, disperse mixed solution with ultrasound wave irradiation, again with this solution of electromagnetic wave radiation;
E, under irradiation and counterflow condition, add alkali lye while stirring, alkali lye adds the back that finishes to be continued electromagnetic wave radiation and refluxes and also stir;
F, with solution cooling, filter, sediment is spent deionised water again with the acetone washing, oven dry promptly obtains required catalyst.
3, preparation method according to claim 2 is characterized in that the salt of metal source described in the steps A is at least a kind of of the nitrate of manganese, iron, copper, zinc, vanadium, rhodium, palladium, gold, platinum or sulfate.
4, preparation method according to claim 2 is characterized in that the titanium source described in the step B is titanium tetrachloride, titanium sulfate or butyl titanate.
5, preparation method according to claim 2 is characterized in that the stabilizing agent described in the step C is sodium acetate or sodium acid carbonate, and its molar concentration is between the 0.001-0.5mol/L, and dosage is that benchmark adds 1-500mL for the solution of originating with every liter of titanium; It is a kind of of trialkylamine or tetraalkylammonium hydroxide or its mixture that structure instructs agent, and molar concentration is 0.001-5mol/L, and its addition is that benchmark adds 1-600mL for the solution of originating with every liter of titanium.
6, preparation method according to claim 2, when it is characterized in that ultrasound wave irradiation dispersion soln described in the step D, supersonic frequency is between the 25KHz-130KHz, ultrasonic time is 5-60min; Wave frequency is 520MHz-280GHz during electromagnetic wave radiation, and the electromagnetic wave input power is 100W-20000W, and exposure time is 1min-30min.
7, preparation method according to claim 2 is characterized in that the alkali lye described in the step e is ammoniacal liquor, NaOH or KOH solution, and the addition of alkali lye is 5-12 for control pH value of solution value; Alkali lye adds the back that finishes to be continued the irradiation backflow and stirs 1-30min.
8, preparation method according to claim 2 is characterized in that the bake out temperature described in the step F is 50-120 ℃.
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